Sodium hydride → HCID 50999543, compound

HRID 546117Notes

Reaction equation

HRID 546117 reaction equation
[N+:1]([C:4]1[CH:8]=[CH:7][NH:6][N:5]=1)([O-:3])=[O:2].[H-].[Na+].Br[CH2:12][CH2:13][O:14][CH3:15]>CN(C)C=O.C(OCC)(=O)C>[CH3:15][O:14][CH2:13][CH2:12][N:6]1[CH:7]=[CH:8][C:4]([N+:1]([O-:3])=[O:2])=[N:5]1

Participants

6

Reactant 3

HCID 24758Sodium hydrideHCID 809722-Bromoethyl methyl etherHCID 178526745HCID 178526745, compound

Product 1

HCID 50999543HCID 50999543, compoundYield 85%

Reagents, catalysts & solvents 2

HCID 6228DimethylformamideSolventHCID 8857Ethyl AcetateSolvent

Procedure

3-Nitro-1H-pyrazole (prepared in example 3, 300 mg, 2.65 mmol) was dissolved in anhydrous N,N-dimethylformamide (6.6 mL) and a 60% dispersion of sodium hydride in mineral oil (106 mg, 2.66 mmol) was added while stirring under nitrogen. After the effervescence ceased and the reaction stirred for an additional 10 min, 1-bromo-2-methoxy-ethane (250 μL, 2.66 mmol) was added. The reaction continued to stir under nitrogen for 16 h. The solution was diluted with ethyl acetate (100 mL), washed with 1.0 M aqueous hydrochloric acid solution (25 mL), water (25 mL), saturated aqueous brine solution (25 mL), dried over magnesium sulfate, filtered and concentrated in vacuo. Purification by flash column chromatography (Merck silica gel 60, 40-63 μm; 40% ethyl acetate/hexanes) afforded 1-(2-methoxy-ethyl)-3-nitro-1H-pyrazole (384 mg, 85%) as a white solid: H1-NMR (400 MHz, CDCl3) δ 3.34 (3H, s), 3.77 (2H, t, J=4.4 Hz), 4.36 (2H, t, J=4.8 Hz), 6.87 (1H, d, J=2.8 Hz), 7.54 (1H, d, J=2.4 Hz).

Workup

  1. stirringthe reaction stirred for an additional 10 min
  2. stirringto stir under nitrogen for 16 h
  3. washwashed with 1.0 M aqueous hydrochloric acid solution (25 mL), water (25 mL), saturated aqueous brine solution (25 mL)
  4. dry with materialdried over magnesium sulfate
  5. filtrationfiltered
  6. concentrationconcentrated in vacuo
  7. customPurification by flash column chromatography (Merck silica gel 60, 40-63 μm; 40% ethyl acetate/hexanes)

Sources & evidence

ORD record
ord-39724536fad24a47b84d0716d10daf8f
Source dataset
uspto-grants-2011_05
Patent number
US07935699B2

Reaction notes

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